Thermoplastic elastomer composition, insulating glass using the composition, process for producing the insulating glass and nozzle for producing the insulating glass

ABSTRACT

A thermoplastic elastomer composition produced from a thermoplastic resin and rubber and having a dispersion phase formed of a rubber composition at least part of which is dynamically crosslinked in the continuous phase of the thermoplastic resin, insulating glass using the thermoplastic elastomer composition as a sealing material and spacer, a process for producing the insulating glass using a sealing material made from the thermoplastic elastomer composition, comprising the steps of inserting the leading end of a charging nozzle into a space between the peripheral portions of a plurality of glass sheets, discharging the sealing material from the leading end of the nozzle body at a predetermined rate, and moving the glass sheets or the nozzle body relative to each other to charge the sealing material made from the thermoplastic elastomer composition into the space between the peripheral portions of the glass sheets, and a nozzle used in this process.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a thermoplastic elastomercomposition having excellent steam permeation resistance and heatdistortion resistance, insulating glass using the composition as asealing material and spacer, a process for producing the insulatingglass and a nozzle for producing the insulating glass.

[0003] 2. Prior Art

[0004] Heretofore, there has been known insulating glass constitutedsuch that a sealing material having a predetermined width is chargedinto a space between the peripheral portions of at least two glasssheets which are opposed to each other in parallel and the hollow layerbetween the glass sheets is isolated from the outside air for thepurpose of an improvement of heat insulating properties, dewcondensation prevention properties and the like.

[0005] This insulating glass has been produced as follows, for example.As shown in FIG. 7, an aluminum spacer 73 filled with a desiccatingagent 72 is placed in a space between the peripheral portions of twoglass sheets 71 a and 71 b which are opposed to each other in paralleland held by a jig or the like to fix a predetermined interval betweenthe glass sheets. Thereafter, a primary sealing material 74 is chargedinto spaces between the both side surfaces of the spacer 73 and theglass sheets 71 a and 71 b, and a two-liquid mixing and normaltemperature curable type secondary sealing material 75, for example by apolysulfide- or silicone-based sealing material, is charged into a spacebetween the spacer 73 and the opening side of the glass sheets 71 and 71b.

[0006] Japanese Patent Application Laid-Open No. Hei 10-158041 disclosesa insulating glass production process and apparatus. In the process andapparatus, a plurality of glass sheets are held in a perpendiculardirection so that the plurality of glass sheets can be simultaneouslymoved in the same direction at the same speed, the glass sheets and adie are moved in different unidirections which are perpendicular to eachother, the glass sheets and the die are moved relative to each otheralternately such that the glass sheets are stopped when the die ismoved, and vice versa, and a resin material is extruded onto theperipheral portions of the glass sheets opposed to each other by movingthe glass sheets and the die alternately for each side of the glasssheets.

[0007] However, since the former production process is carried out byusing a jig, spacer and the like, the work becomes complicated and takesmuch time and labor. On the other hand, the latter process has such aproblem that it is difficult to obtain insulating glass having goodappearance because the resin material cannot be paved nicely when it isextruded.

[0008] In the insulating glass using the normal temperature curablesealing material in the prior art processes, it takes time to cure thesealing material and a final product cannot be promptly shipped.Especially in winter, the sealing material must be placed in a heatingchamber for curing.

[0009] Therefore, it is desired to improve productivity by simplifyingthe process for producing insulating glass and shortening the cure time.

[0010] In contrast to this, Japanese Patent Application Laid-Open Nos.Hei 10-110072, Hei 10-114551, Hei 10-114552 and the like propose aninvention in which a resin containing a desiccating agent as required isused as a spacer and sealing material in place of the aluminum spacer.The spacer/sealing material proposed in these publications is acomposition containing butyl-based rubber and crystalline polyolefinwhich are preferably mixed at a high temperature.

[0011] In insulating glass using this composition, the compositionserves as a resin spacer and a sealing material. Insulating glass can beproduced in which the peripheral portions of the glass sheets are sealedup by paving the composition on the peripheral portions of two glasssheets opposed to each other with a spacer therebetween. Thus, theproduction process is simplified. However, in this insulating glass, theglass sheets are not dislocated each other when a load is placed uponthe glass sheets at normal temperature but the glass sheets aredislocated each other while a high-temperature sealing material is pavedand cured especially when the insulating glass is produced or when thetemperature of the outside air rises in summer or by sunlight after theinsulating glass is formed into a construction material or the likebecause the composition which serves as a sealing material and resinspacer contains a small amount of a resin in rubber and hence, is easilydeformed at high temperatures.

SUMMARY OF THE INVENTION

[0012] It is a first object of the present invention to provide athermoplastic elastomer composition which has excellent steam permeationresistance and heat distortion resistance and is suitable for use as asealing material and spacer for insulating glass.

[0013] It is a second object of the present invention to provideinsulating glass which uses the thermoplastic elastomer composition as asealing material and spacer, is produced easily, has excellent steampermeation resistance and is not deformed in the entire shape by thedislocation of the glass sheets when it is allowed to cool after thesealing material and spacer is paved, or after processing or at hightemperatures in summer or the like.

[0014] It is a third object of the present invention to provide aprocess for producing insulating glass which enables a sealing materialto be efficiently paved in a space between the peripheral portions ofglass sheets and leveled to obtain good appearance and reduces thenumber of working steps to carry out efficient work.

[0015] It is a fourth object of the present invention to provide anozzle for producing insulating glass which can be advantageously usedin the above process for producing insulating glass.

[0016] The inventor of the present invention has conducted intensivestudies to solve the above problems and have found that the aboveobjects can be attained by a thermoplastic elastomer compositioncontaining a continuous phase formed of a thermoplastic resin having awater vapor permeability below a predetermined value and a dispersionphase formed by dynamically crosslinking a rubber component having awater vapor permeability below a predetermined value after crosslinking,and insulating glass using the composition as a sealing material andspacer. Thus, the present invention has been accomplished based on thisfinding.

[0017] To attain the first object, the present invention provides athermoplastic elastomer composition which is produced from athermoplastic resin having a water vapor permeability of 100 g/m²·24 hor less (30 μm in thickness) and rubber having a water vaporpermeability of 300 g/m²·24 h or less (30 μm in thickness) whencrosslinked and which has a dispersion phase formed of a rubbercomposition at least part of which is dynamically crosslinked in thecontinuous phase of the thermoplastic resin.

[0018] To attain the second object, the present invention providesinsulating glass which uses the thermoplastic elastomer composition as asealing material and spacer.

[0019] To attain the third object, the present invention provides aprocess for producing insulating glass by charging a sealing materialhaving a predetermined width into a space between the peripheralportions of at least two glass sheets which are opposed to each other inparallel at a predetermined interval to isolate the hollow layer fromthe outside air, the process comprising the steps of inserting inadvance the leading end of a charging nozzle into a space between theperipheral portions of a plurality of glass sheets, contacting a slideplate provided at the top of the leading end portion of the nozzle tothe peripheral portions of the plurality of glass sheets, discharging asealing material from the leading end of the nozzle body at apredetermined rate, and moving at least one of the glass sheets and thenozzle body relative to the other to charge the sealing material fromthe leading end portion of the nozzle into the space between theperipheral portions of the glass sheets.

[0020] To attain the fourth object, the present invention provides anozzle for producing insulating glass by inserting the leading endportion of the nozzle into a space between the peripheral portions of atleast two glass sheets which are opposed to each other in parallel at apredetermined interval, and charging a sealing material from the leadingend portion of the nozzle into the space between the peripheral portionsof the glass sheets while at least one of the glass sheets and thenozzle body is moved relative to the other, wherein the leading end ofthe nozzle body has a width for positioning the interval between theplurality of glass sheets, and a slide plate which slides along theperipheral portions of the plurality of glass sheets and is provided atthe top of the leading end portion.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] These and further features of the present invention will beapparent with reference to the following description and drawings,wherein:

[0022] FIGS. 1(a) and (b) are schematic sectional views of insulatingglass according to an embodiment of the present invention;

[0023]FIG. 2 is a perspective view of a nozzle for producing insulatingglass of the present invention;

[0024]FIG. 3 is a side view of the nozzle for producing insulating glassof the present invention;

[0025]FIG. 4 is a plan view of the nozzle for producing insulating glassof the present invention;

[0026]FIG. 5 is a perspective view showing that a sealing material ischarged into a space between the peripheral portions of two glasssheets;

[0027]FIG. 6 is a sectional view of a cup for measuring water vaporpermeability; and

[0028]FIG. 7 is a diagram for explaining the insulating glass productionprocess of the prior art.

DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention will be described in detail hereinunder.

[0030] The thermoplastic elastomer composition of the present invention(to be referred to as “composition of the present invention”hereinafter) is suitable for use as a sealing material and spacer forinsulating glass and has a continuous phase formed of a thermoplasticresin and a dispersion phase formed of a rubber composition at leastpart of which is dynamically crosslinked. The dispersion phase isuniformly dispersed in the continuous phase.

[0031] A thermoplastic resin having a water vapor permeability of 100g/m²·24 h or less when a sheet having a thickness of 30 μm is formedfrom the thermoplastic resin alone is used as the thermoplastic resinwhich is one of the components of the composition of the presentinvention.

[0032] Illustrative examples of the thermoplastic resin includepolyolefin-based resins such as high-density polyethylene (HDPE),low-density polyethylene (LDPE), ultra high molecular weightpolyethylene (UHMWPE), isotactic polypropylene, syndiotacticpolypropylene and ethylene-propylene copolymer resins; polyamide-basedresins such as nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11(Nil), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66copolymer (N6/66), nylon 6/66/610 copolymer (N6/66/610), nylon MXD6(MXD6), nylon 6T, nylon 6/6T copolymer, nylon 66/PP copolymer and nylon66/PPS copolymer; polyester-based resins such as aromatic polyestersexemplified by polybutylene terephthalate (PBT) and polyethyleneterephthalate (PET); polyether-based resins such as polyphenylene oxide(PPO), modified polyphenylene oxide (modified PPO), polysulfone (PSF)and polyether ether ketone (PEEK); polymethacrylate-based resins such asmethyl polymethacrylate (PMMA) and ethyl polymethacrylate;polyvinyl-based resins such as a vinyl alcohol/ethylene copolymer(EVOH), polyvinylidene chloride (PVDC) and vinylidene chloride/methylacrylate copolymer; fluororesins such as polyvinylidene fluoride (PVDF),polychlorofluoroethylene (PCTFE) and polyacrylonitrile resin (PAN); andthe like.

[0033] Out of these, polyolefin-based resins, polyester-based resin,polyether-based resin and fluororesins having a heat distortiontemperature of 50° C. or more are preferred because the composition ofthe present invention obtained therefrom has excellent moldability andexcellent heat distortion resistance against the temperature of theoutside air or the like when it is used as a sealing material and spacerfor insulating glass which will be described hereinafter, so that areduction in water vapor permeability caused by water absorption can beminimized.

[0034] The dispersion phase dispersed in the continuous phase of thecomposition of the present invention is formed of a rubber compositionat least part of which is dynamically crosslinked. Rubber having a watervapor permeability of 300 g/m²·24 h or less when a sheet having athickness of 30 μm is produced by crosslinking only a rubber componentis used as a rubber component which is the main constituent ingredientof this dispersion phase. Illustrative examples of the rubber componentinclude cyclic NR, ethylene propylene rubber (EPDM, EPM),polyisobutylene, IIR, Br-IIR, CI-IIR, halide of a paramethylstyrene-polyisobutylene copolymer (X-IPMS), ethylene-vinyl acetaterubber (EVA), chlorinated polyethylene, chlorosulfonated polyethylene,acrylonitrile butadiene rubber and hydride thereof, hydrin rubber andthe like. Out of these, ethylene propylene rubber, IIR, Br-IIR andX-IPMS are preferred from the viewpoints of heat resistance at the timeof kneading with a resin, low water vapor permeability and crosslinkingreactivity.

[0035] Further, a reinforcement, filler, softening agent, crosslinkingagent, age resistor, processing aid and the like which are generallyblended to improve the dispersibility, heat resistance and the like ofthe rubber composition and for other purposes may be suitably blendedinto the rubber composition forming the dispersion phase.

[0036] A combination of a thermoplastic resin forming the continuousphase and rubber which is the main constituent ingredient of thedispersion phase of the composition of the present invention is notparticularly limited and at least one thermoplastic resin selected fromthe above thermoplastic resins and at least one rubber selected from theabove rubbers may be used in combination.

[0037] The weight ratio of the thermoplastic resin composition to therubber composition constituting the composition of the present inventionis not particularly limited but preferably 85/15 to 15/85, morepreferably 50/50 to 30/70.

[0038] The criticality of this ratio is dependent upon the volume ratioand viscosity ratio of the thermoplastic resin composition to the rubbercomposition.

[0039] The rubber composition is the dispersion phase and thethermoplastic resin composition is the continuous phase of thecomposition of the present invention. Even when the both components aresimply kneaded together while they are molten, a thermoplastic elastomercomposition having a dispersion structure of interest is not alwaysobtained. The relationship between the melt viscosity of thethermoplastic resin composition to the melt viscosity of the rubbercomponent at their kneading temperature is adjusted by controlling thevolume ratio of the both components to be blended so that the value ofα₁ obtained from the following equation should become less than 1.

α₁=(φ_(R)/φ_(P))×(η_(P)/η_(R))

[0040] where Φ_(R) is the volume fraction of the rubber composition,φ_(P) is the volume fraction of the thermoplastic resin composition,η_(P) is the melt viscosity (poise) of the rubber composition at atemperature and a shearing speed at which the thermoplastic resincomposition and the rubber composition are kneaded together, and η_(R)is the melt viscosity (poise) of the thermoplastic resin composition ata temperature and a shearing speed at which the thermoplastic resincomposition and the rubber composition are kneaded together.

[0041] When the value of α₁ is 1 or more, the dispersion structure ofthe composition of the present invention may be inverted and the rubbercomposition may be the continuous phase of the composition.

[0042] 0.5≦η_(R)/η_(P)≦3.0 is preferred. Within this range, the rubbercomposition is dispersed in the thermoplastic resin as particles havinga size of about 0.1 μm to several tens of μm.

[0043] In the present invention, the term “melt viscosity” means themelt viscosity of each component at an arbitrary temperature when it iskneaded. Since the melt viscosity of a polymer component changesaccording to temperature, shearing speed (sec⁻¹) and shearing stress, itis obtained from the following equation by flowing the polymer componentin a molten state in a thin tube at an arbitrary temperature at whichthe component is molten, particularly at a temperature range at the timeof kneading and measuring stress and shearing speed.

η=σ/{dot over (γ)}

[0044] where σ is a shearing stress and {dot over (γ)} is a shearingspeed.

[0045] The capillary rheometer capillograph 1C of Toyo Seiki Co., Ltd.may be used as an example for the measurement of melt viscosity.

[0046] The composition of the present invention may contain a moistureabsorbent. When the composition of the present invention is used as asealing material or spacer for insulating glass, particularly a sealingmaterial and spacer, it preferably contains a moisture absorbent.

[0047] The expression “sealing material and spacer” means that thecomposition of the present invention is used as a spacer arranged in aspace between the peripheral portions of the opposed glass sheets ofinsulating glass to ensure the thickness of an air layer for theinsulating glass and that the spacer is press-contacted to the glasssheets without paving a sealing material between the spacer and theglass sheets so that the composition of the present invention is used asa sealing material for isolating the air layer from the outside air.That is, when the composition of the present invention is used as asealing material and spacer, it serves as a spacer and a sealingmaterial at the same time.

[0048] The composition of the present invention may be used as a sealingmaterial for insulating glass and used in combination with other spacer,or may be used as a spacer and used in combination with other sealingmaterial.

[0049] The composition of the present invention preferably contains amoisture absorbent. When the composition of the present invention isused as a sealing material and spacer for insulating glass, it iseffective because it can absorb moisture contained in the air layerformed between the two glass sheets, dry the air layer, absorb waterentering from the outside of the insulating glass and prevent a rise inthe dew point of air sealed in the air layer. The expression “dew pointin the insulating glass” means the highest temperature at which dewcondensation on the inner surface of the insulating glass is visuallyobserved.

[0050] A moisture absorbent which is generally charged in the metalspacer or the like of insulating glass may be used as the moistureabsorbent, as exemplified by synthetic zeolite, silica gel, alumina andthe like.

[0051] The amount of the moisture absorbent is preferably 10 to 70 partsby weight based on 100 parts by weight of the total of polymercomponents (a thermoplastic resin and rubber) of the present invention.Within this range, a composition having excellent hygroscopicity can beobtained.

[0052] Further, the composition of the present invention preferablycontains a steam permeable barrier resin (to be referred to as “barrierresin” hereinafter). The composition of the present invention hasexcellent steam permeation resistance because the thermoplastic resinwhich is the continuous phase of the composition and rubber which is themain constituent ingredient of the dispersion phase have a water vaporpermeability below respective predetermined values. However, when thecomposition of the present invention contains a barrier resin, the steampermeation resistance of the obtained composition of the presentinvention is further improved.

[0053] The term “barrier resin” used herein means a resin which has asmaller water vapor permeability than that of the thermoplastic resinwhich is the continuous phase, can be a barrier by increasing itscrystallinity even if it is the same type of a resin as thethermoplastic resin of the continuous phase, which is preferably kneadedinto the continuous phase in layers in a lamellar form when it iskneaded into the thermoplastic elastomer composition of the presentinvention and which is desirably lamellar in shape with an aspect ratioof 10 to 500 (aspect ratio: a/b where a is the length of a long axis andb is the length of a short axis).

[0054] In insulating glass which uses the composition of the presentinvention as a sealing material and spacer which will be describedhereinafter, the barrier resin is preferably existent in the continuousphase of the composition of the present invention and dispersed as alamellar product parallel to the peripheral surfaces of the insulatingglass. The barrier resin dispersed in layers is effective in preventingthe permeation of steam and reducing water vapor permeability.

[0055] Illustrative examples of a resin component constituting thebarrier resin include polyolefins such as high-density polyethylene(HDPE) and ultra high molecular weight polyethylene (UHMWPE), polyamideresins such as nylon 6, nylon 66 and aromatic nylon (MXD6), polyesterresins such as polyethylene terephthalate (PET), polyvinyl resins suchas ethylene-vinyl alcohol (EVOH), polyvinyl chloride resins,polyvinylidene chloride (PVDC) resins and the like. In the presentinvention, these barrier resins may be used alone or in combination oftwo or more.

[0056] When the composition of the present invention contains a barrierresin, the content of the barrier resin is suitably determined such thatthe melt viscosities and volume fractions of the thermoplastic elastomercomposition which is the composition of the present invention excludingthe barrier resin, and the barrier resin should satisfy the followingexpressions (1) and (2). The weight ratio of the above thermoplasticelastomer composition to the barrier resin is generally 90/10 to 50/50,particularly preferably 90/10 to 70/30.

η_(d)/η_(m)≧2.0  (1)

α₂=Φ_(d)/Φ_(m)×η_(m)/η_(d)<1.0  (2)

[0057] where η_(d) is the melt viscosity (poise) of the barrier resin,η_(m) is the melt viscosity (poise) of the thermoplastic elastomercomposition, Φ_(d) is the volume fraction of the barrier resin, andΦ_(m) is the volume fraction of the thermoplastic elastomer composition.

[0058] In the expression (1), when the value of η_(d)/η_(m) is less than2, the barrier resin is finely dispersed in the thermoplastic elastomercomposition while it is molten and kneaded and its function as a barrierbecomes reduced. The value of η_(d)/η_(m) is preferably 3 or more. Inthe expression (2), when α₂ is less than 1, the barrier resin can beexistent as a dispersion phase in the continuous phase formed of thethermoplastic elastomer composition, more specifically, in thethermoplastic resin composition forming the continuous phase of thethermoplastic elastomer composition.

[0059] A filler such as talc, calcium carbonate, mica or carbon black,tackifier such as rosin ester and coumarone resin, age resistor, thermalstabilizer, antioxidant, softening agent, processing aid agent and otheradditives may be added to the composition of the present invention inlimits that do not impair the object of the present invention in orderto improve fluidity, heat resistance, physical strength, costperformance and the like. Further, an inorganic pigment and organicpigment may be blended into the thermoplastic resin composition forcoloration.

[0060] Moreover, an adhesion promoter may be added to the composition ofthe present invention to improve adhesion to glass. The adhesionpromoter is a silane coupling agent such as vinylsilane,methacrylsilane, aminosilane, epoxysilane or mercaptosilane, or apolymer having a maleic acid group, carboxylic acid group, hydroxylgroup or epoxy group. Specific examples of the adhesion promoter includemaleic acid modified polyethylene, maleic acid modified polypropylene,maleic acid modified ethylene ethyl acrylate, epoxy modifiedstyrene-butadiene copolymer, epoxy modified ethylene-vinyl acetatecopolymer, ethylene-vinyl acetate copolymer and saponified productsthereof.

[0061] When the chemical compatibilities of the above specificthermoplastic resin composition and rubber composition are differentfrom each other, an appropriate compatibilizing agent is preferably usedas a third component to compatibilize the both materials. Theinterfacial tension between the thermoplastic resin composition and therubber composition is reduced by mixing a compatibilizing agent, withthe result that the characteristic properties of the both compositionsare developed more effectively as the particle diameter of the rubbercomposition forming the dispersion phase becomes very small. Thecompatibilizing agent is generally a copolymer having both structures ofa resin component and a rubber component or either one of them, or acopolymer having an epoxy group, carboxyl group, carbonyl group, halogengroup, amino group, oxazoline group or hydroxyl group which can reactwith a resin component or rubber component. They can be selectedaccording to the types of the resin component and the rubber componentto be mixed together.

[0062] General-purpose compatibilizing agents include astyrene-ethylene-butylene-styrene-based block copolymer (SEBS) andmaleic acid modified product thereof, EPDM, EPM and maleic acid modifiedproducts thereof, EPDM/styrene and EPDM/acrylonitrile graft copolymerand maleic acid modified products thereof, styrene/maleic acidcopolymer, reactive phenoxthine and the like.

[0063] When a compatibilizing agent is blended into the composition ofthe present invention, its amount is not particularly limited butpreferably 0.5 to 20 parts by weight based on 100 parts by weight of thetotal of polymer components (the thermoplastic resin and rubber).

[0064] In the present invention, a vulcanizing agent, vulcanizingaccelerator, vulcanization conditions (temperature and time) and thelike used for the dynamic crosslinking of the rubber composition may besuitably determined according to the composition of the rubbercomposition used and are not particularly limited. A general rubbervulcanizing agent (crosslinking agent) may be used as the vulcanizingagent.

[0065] Illustrative examples of sulfur-based vulcanizing agents used asthe rubber vulcanizing agent include powdery sulfur, precipitatingsulfur, highly dispersible sulfur, surface treated sulfur, insolublesulfur, dimorpholine sulfide, alkylphenol disulfide and the like.

[0066] When this sulfur-based vulcanizing agent is used, its amount ispreferably 0.5 to 4 phr (parts by weight based on 100 parts by weight ofthe rubber component, this shall apply thereafter).

[0067] Organic peroxide-based vulcanizing agents include benzoylperoxide, t-butylhydro peroxide, 2,4-dichlorobenzoyl peroxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane and2,5-dimethylhexane-2,5-di(peroxybenzoate).

[0068] When this organic peroxide-based vulcanizing agent is used, itsamount is preferably 1 to 15 phr.

[0069] Further, phenol resin-based vulcanizing agents include bromidesof alkylphenol resins, mixed crosslinking vulcanizing agents containinga halogen doner such as tin chloride or chloroprene and an alkylphenolresin.

[0070] When this phenol resin-based vulcanizing agent is used, itsamount is preferably 1 to 20 phr.

[0071] Other vulcanizing agents include zinc oxide (about 5 phr),magnesium oxide (about 4 phr), litharge (about 10 to 20 phr), p-quinonedioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone,poly-p-dinitrosobenzene (about 2 to 10 phr) and methylindianiline (about0.2 to 10 phr).

[0072] The composition of the present invention may contain avulcanizing accelerator as required. A general vulcanizing acceleratorsuch as aldehyde-ammonia-based, guanidine-based, thiazole-based,sulfenamide-based, thiuram-based, dithionate-based or thiourea-basedgeneral vulcanizing accelerator may be used in an amount of about 0.5 to2 phr.

[0073] Illustrative examples of the vulcanizing accelerator includehexamethylenetetramine as the aldehyde-ammonia-based vulcanizingaccelerator, diphenylguanidine as the guanidine-based vulcanizingaccelerator, dibenzothiazyldisulfide (DM), 2-mercaptobenzothiazole andZn salts and cyclohexylamine salts thereof as the thiazole-basedvulcanizing accelerator, cyclohexylbenzothiazyl sulfenamide (CBS),N-oxydiethylenebenzothiazyl-2-sulfenamide, N-t-butyl-2-benzothiazolesulfenamide and 2-(thymolpolynildithio)benzothiazole as thesulfenamide-based vulcanizing accelerator, tetramethylthiuram disulfide(TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide(TMTM) and dipentamethylenethiuram tetrasulfide as the thiuram-basedvulcanizing accelerator, Zn-dimethyl dithiocarbamate, Zn-diethyldithiocarbamate, Zn-di-n-butyl dithiocarbamate, Zn-ethylphenyldithiocarbamate, Tc-diethyl dithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyl dithiocarbamate and pipecolinepipecolyldithiocarbamate as the dithionate-based vulcanizing accelerator, andethylene thiourea and diethyl thiourea as the thiourea-based vulcanizingaccelerator.

[0074] A general rubber auxiliary such as zinc oxide (about 5 phr),stearic acid, oleic acid or Zn salt thereof (about 2 to 4 phr) may alsobe used as the vulcanizing accelerator.

[0075] The composition of the present invention is prepared bypreviously supplying a thermoplastic resin component and an unvulcanizedrubber composition to a kneader such as a double-screw kneader to meltand knead these compositions and dispersing the rubber composition inthe thermoplastic resin composition forming a continuous phase (matrixphase) as a dispersion phase (domain). Thereafter, a thermoplasticelastomer composition can be produced by adding a vulcanizing agentunder kneading to dynamically crosslink the rubber composition. Theaddition of compounding additives to the thermoplastic resin compositionor rubber composition may be carried out during kneading but preferablycarried out before kneading. A vulcanizing agent is mixed into therubber composition in advance so that the rubber composition can becrosslinked while the thermoplastic resin composition and the rubbercomposition are kneaded together.

[0076] The kneader used for the kneading of the thermoplastic resincomposition and the rubber composition is not particularly limited and ascrew extruder, kneader, Banbury mixer, double-screw kneading extruderand the like may be used. Particularly for the kneading of thethermoplastic resin composition and the rubber composition and thedynamic crosslinking of the rubber composition, a double-screw kneadingextruder is preferably used. Two or more kneaders may be used to kneadthese compositions sequentially.

[0077] As for melt kneading conditions, the temperature may be higherthan the melting temperature of the thermoplastic resin. When a barrierresin is blended, the temperature may be higher than the meltingtemperature of the thermoplastic resin and lower than the heatdistortion temperature of the barrier resin. The shearing speed at thetime of kneading is preferably 500 to 7,500 sec⁻¹. The total kneadingtime is 30 seconds to 10 minutes and the vulcanizing time after additionis preferably 15 seconds to 5 minutes.

[0078] The prepared thermoplastic elastomer composition is then extrudedinto a strand form from the kneading extruder, cooled with water or thelike, pelletized by a pelletizer for resins and then may be molded. Thehigh-temperature thermoplastic elastomer composition thus prepared maybe directly paved and charged into a space surrounded by the peripheralportions of the glass sheets of the insulating glass and a previouslyinstalled spacer as a sealing material for the insulating glass.

[0079] Alternatively, the prepared thermoplastic elastomer compositionmay be molded into the form of a spacer by extrusion molding, injectionmolding or the like. In this case, when the high-temperaturethermoplastic elastomer composition discharged from a molding machine isused, adhesion to the glass sheets and the spacer is advantageouslyincreased.

[0080] When the composition of the present invention contains a barrierresin, pellets obtained by molding the thermoplastic elastomercomposition prepared as described above and the pellets of the abovebarrier resin are mixed in a predetermined ratio. The mixing of thepellets is carried out by dry blending with a commonly used blender orthe like, or by supplying the pellets into a kneader from independentfeeders in a predetermined ratio.

[0081] The mixture of the both pellets is melt kneaded at a low shearingspeed (for example, 30 sec⁻¹ or more and less than 300 sec⁻¹), such thatthe thermoplastic elastomer composition and the barrier resin are meltkneaded in a single-screw extruder and the resulting mixture is extrudedfrom the end of the extruder or injection molded, and the resulting meltkneaded product is directly supplied into a molding machine to produce asealing material and spacer. Alternatively, the kneaded product may beextruded into a strand form from the end of the extruder, pelletized andmolded.

[0082] When the composition of the present invention is used as asealing material, spacer, or a sealing material and spacer, the barrierresin is preferably aligned in lamellar layers parallel to theperipheral surfaces of the insulating glass. In order to align thebarrier resin like this, it is effective to make flat the shape of thenozzle for extruding the composition of the present invention forinjection or to set the shearing speed at the outlet of the extruder at30 to 300 s⁻¹.

[0083] In the composition of the present invention obtained from theabove components and by the above production process, the dynamicallycrosslinked rubber composition forms a dispersion phase in thethermoplastic resin composition forming a continuous phase. That is, inthe above production process, the crosslinking of the rubber compositionproceeds while the thermoplastic resin composition and the rubbercomposition are kneaded together so that the obtained compositioncontains the crosslinked rubber as a dispersion phase finely dispersedin the resin composition as a continuous phase.

[0084] In a composition obtained merely by kneading the thermoplasticresin with rubber, rubber is dispersed as fine particles immediatelyafter they are kneaded and provided with large shearing force but rubberturns back to a large mass when kneading is stopped with the result thatthe rubber may form a continuous phase and the thermoplastic resin maybe dispersed in the rubber. A composition having this structure has lowheat distortion resistance because the rubber forms a continuous phase.

[0085] The composition of the present invention has excellent steampermeation resistance. The composition of the present invention in whichrubber is finely dispersed in the thermoplastic resin has also excellentheat distortion resistance.

[0086] The composition of the present invention containing a moistureabsorbent has excellent hygroscopicity.

[0087] The composition of the present invention comprising athermoplastic resin having a heat distortion temperature of 70° C. ormore as a continuous phase is excellent in heat distortion resistanceand also processability when the composition of the present invention isprocessed into a sealing material or the like.

[0088] Further, the composition of the present invention containing asteam permeable barrier resin is more superior in steam permeationresistance.

[0089] A description is subsequently given of insulating glass whichuses the composition of the present invention as a sealing material andspacer.

[0090] FIGS. 1(a) and 1(b) are schematic sectional views in a directionperpendicular to glass sheets of the insulating glass of the presentinvention. In the insulating glass 10 shown in FIGS. 1(a) and 1(b), aspacer 3 for determining the interval between two opposed glass sheets 1a and 1 b is installed between the two glass sheets 1 a and 1 b to forman air layer 2 having a predetermined volume therebetween. This spacer 3may be made from a metal such as aluminum and a sealing material madefrom the composition of the present invention may be installed as aseparate unit, but the spacer 3 is preferably made from the compositionof the present invention. The hardness of the spacer made from thecomposition of the present invention is 25 to 90 in terms of JIS Ahardness. Within this range, even when stress is applied to the adhesivesurfaces between the glass sheets and the spacer by a rise in thetemperature of the air layer 2, it can be avoided that the glass isbroken if bonding strength is high and the glass sheets and the spacerare separated from each other if bonding strength is insufficient.Further, within this range, the insulating glass is not deformed by theweight of the glass sheets.

[0091] The interval between the glass sheets 1 a and 1 b is generallyabout 6 mm or about 12 mm. The insulating glass 10 shown in FIGS. 1(a)and 1(b) comprises two glass sheets. The number of the glass sheets isnot limited to two but two or more glass sheets may be used and thenumber of the glass sheets can be selected as required.

[0092] In the insulating glass of the present invention shown in FIGS.1(a) and 1(b), the spacer 3 also serves as a sealing material forsealing up the space between the two glass sheets 1 a and 1 b from theoutside air and holding the glass sheets. The spacer 3 prevents waterfrom entering from the outside without using a primary sealing material,a secondary sealing material and the like and serves as a spacer andsealing material for holding the two glass sheets 1 a and 1 b at apredetermined interval.

[0093] The insulating glass of the present invention may have adhesivelayers 4 between the spacer 3 which also serves as a sealing materialand the glass sheets 1 a and 1 b as shown in FIG. 1(b). When theinsulating glass of the present invention has the adhesive layers 4,adhesion between the spacer 3 and the glass sheet 1 a or 1 b can beimproved, the entry of water from the outside of the insulating glasscan be prevented, and a rise in the dew point of the air layer 2 can besuppressed.

[0094] A glass sheet for use in construction materials, vehicles or thelike can be used as the glass sheet of the insulating glass of thepresent invention, as exemplified by glass which is generally used inwindows, reinforced glass, wire-net glass, heat absorbing glass, heatreflecting glass, organic glass and the like. The thickness of the glasssheet is suitably determined.

[0095] An adhesive used in the adhesive layer 4 is a silane couplingagent such as vinylsilane, methacrylsilane, aminosilane, epoxysilane ormercaptosilane, or a polymer having a maleic acid group, carboxylic acidgroup, hydroxyl group, epoxy group or the like. Illustrative examples ofthe adhesive include maleic acid modified polyethylene, maleic acidmodified polypropylene, maleic acid modified ethylene ethyl acrylate,epoxy modified styrene-butadiene copolymer, epoxy modifiedethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer andsaponified products thereof. Out of these, olefin-vinyl acetatecopolymers are preferred. Illustrative examples of the olefin includeethylene, propylene, butene and the like. Out of these, anethylene-vinyl acetate copolymer is preferred from the viewpoint ofadhesion to glass and water resistance. The above olefin-vinyl acetatecopolymer is preferably saponified because the saponified product hashigh reactivity and improved adhesion.

[0096] The insulating glass of the present invention can be basicallyproduced by extruding the composition of the present invention through anozzle or the like connected to an extruder into a space between twofixed parallel glass sheets and bonding it to the glass sheets. Theinner sides of the peripheral portions of the glass sheets 1 a and 1 bto which the spacer 3 is bonded can be coated with a primer as requiredand further an adhesive as required. As the case may be, the compositionof the present invention is extruded onto the inner side of theperipheral portion of one of the two glass sheets and the other glasssheet is press-bonded to the composition of the present invention beforethe composition does not become cool. To coat the primer and theadhesive, they may be coated manually with an applicator or the like, orautomatically using a robot for extruding the primer and the adhesive.

[0097] Particularly, the composition of the present invention and theadhesive are co-extruded by an extruder such that the adhesive forms anouter layer and the composition of the present inventor forms an innerlayer and then molded into a spacer having a predetermined shape.Alternatively, the extruded composition of the present invention and theextruded adhesive may be directly discharged into the space between theperipheral portions of the glass sheets.

[0098] The composition of the present invention for forming a spacer,which has a high temperature after kneading, is preferably used evenwhen it is molded into a spacer and installed between the glass sheetsand even when it is directly discharged into the space between the glasssheets from an extruder. This is because strong adhesion between thespacer and the glass sheets can be obtained.

[0099] The insulating glass of the present invention constituted asdescribed above is produced very easily because the number of productionsteps is greatly reduced compared with conventional insulating glasswhich is produced using a metal spacer and a sealing material.

[0100] Since the composition of the present invention is used as asealing material and spacer, it does not take long to cure it unlike theconventional two-liquid type sealing material and hence, productivity ishigh. Since the composition of the present invention has excellent steampermeation resistance as described above, the insulating glass of thepresent invention has a low dew point. Further, since the composition ofthe present invention has excellent heat distortion resistance, evenwhen the temperature of the glass sheets becomes high due to thetemperature of the outside air or the like, the insulating glass is notdeformed by the dislocation of the glass sheets.

[0101] In the insulating glass which uses the composition of the presentinvention containing a moisture absorbent and a barrier resin, the airlayer can be held while it is dry, the entry of water from the outsidecan be prevented, and the dew point is maintained at a low level.

[0102] Further, out of the above processes for producing the insulatingglass of the present invention, preferred is a process which comprisesthe steps of inserting in advance the leading end of the charging nozzleinto the space between the peripheral portions of a plurality of glasssheets, contacting a slide plate provided at the top of the leading endportion of the nozzle to the peripheral portions of the plurality ofglass sheets, discharging a sealing material from the leading end of thenozzle body at a predetermined speed, and moving at least either one ofthe glass sheets and the nozzle body relative to the other to charge thesealing material into the space between the peripheral portions of theglass sheets from the leading end of the nozzle. According to thisprocess, the sealing material can be efficiently paved in the spacebetween the peripheral portions of the glass sheets and the sealingmaterial can be leveled to obtain good appearance, and efficient workcan be carried out by reducing the number of working steps.

[0103] Further, a production nozzle having a width for positioning theinterval between the plurality of glass sheets at the leading end of thenozzle body and having a slide plate which slides along the peripheralportions of the plurality of glass sheets at the top of the leading endportion is preferably used in this process.

[0104] This process will be described hereinunder with reference toFIGS. 2 to 6.

[0105]FIG. 2 is a perspective view of a nozzle 20 for producinginsulating glass which is inserted between the peripheral portions oftwo glass sheets 1 a and 1 b which are opposed to each other in paralleland held by an unshown jig or the like, FIG. 3 is a side view of theproduction nozzle 20 and FIG. 4 is a plan view of the production nozzle20.

[0106] The production nozzle 20 has a passage 12 for discharging asealing material W in a nozzle body 11 having an L-shaped section, atleast the leading end portion 11 a of the nozzle 20 has a width H forpositioning the interval h between a plurality of glass sheets 1 a and 1b, and a slide plate 13 which slides along the peripheral portions lx ofthe plurality of glass sheets 1 a and 1 b is integrally provided on theupper surface of the leading end portion 11 a.

[0107] The slide plate 13 projects along the discharge direction(direction shown by an arrow Q) of the sealing material W, and a guideplate 14 is formed at a lower end portion at the leading end of thenozzle body 20 in such a manner that the guide plate 14 is substantiallyparallel to the slide plate 13 and projects along the dischargedirection of the sealing material W. The rear end portion 11 b of thenozzle body 11 is connected to an unshown sealing material W feeder.

[0108] In the process for producing the insulating glass using thisproduction nozzle 20, as shown in FIG. 2, the leading end portion 11 aof the nozzle body 11 is first inserted into the space between theperipheral portions of two glass sheets 1 a and 1 b which are opposed toeach other in parallel at a predetermined interval and held by anunshown jig or the like, and the sealing material W is charged into thespace between the peripheral portions of the glass sheets from theleading end portion 11 a of the nozzle at a predetermined deliverypressure (for example, 15 MPa) or a predetermined delivery rate (forexample, 2,000 g/min) while at least one of the glass sheets 1 a and 1 band the nozzle body 11 is moved relative to the other.

[0109] That is, the nozzle body 11 is moved along the peripheralportions lx of the glass sheets 1 a and 1 b while the glass sheets 1 aand 1 b are fixed at predetermined positions, or the glass sheets 1 aand 1 b are moved at a predetermined speed while the nozzle body 11 isfixed. Or the nozzle body 11 and the glass sheets 1 a and 1 b are movedin opposite directions at the same speed, while the sealing material Wis supplied into the discharge passage 12 in the nozzle body 11 from thesealing material W feeder and charged into the space between theperipheral portions of the glass sheets 1 a and 1 b.

[0110] When the sealing material W is charged while at least one of theglass sheets 1 a and 1 b and the nozzle body 11 is moved relative to theother, the slide plate 13 provided at the top of the leading end portionof the nozzle body 11 is contacted to the peripheral portions 1 x of theplurality of glass sheets 1 a and 1 b and slid (the sealing material Qis flatly pressed with a so-called knife), whereby the sealing materialW at the peripheral portions 1 x of the glass sheets 1 a and 1 b can beleveled, and at the same time, the lower side of the sealing material inthe space between the glass sheets 1 a and 1 b can be leveled by theguide plate 14 provided at the low end portion at the leading end of thenozzle body 11 as shown in FIG. 5.

[0111] The sealing material used in this process preferably has an MFR(melt flow rate) of 20 to 500 g/10 min.

[0112] According to the above process, the sealing material W can beefficiently paved in the space between the peripheral portions of theglass sheets 1 a and 1 b by charging the sealing material W into thespace between the peripheral portions of the glass sheets 1 a and 1 bfrom the leading end of the nozzle body 11 and leveled to obtain goodappearance, and efficient work can be carried out by reducing the numberof working steps.

[0113] In the above process, the method of charging the sealing materialW into the space between the two glass sheets 1 a and 1 b has beendescribed. However, the sealing material W can be charged into spacesamong two or more glass sheets by transforming and processing the nozzlebody 11.

EXAMPLE

[0114] The following examples are given to further illustrate thethermoplastic elastomer composition, insulating glass, a process forproducing the insulating glass and a nozzle of the present invention.

Examples 1 to 10 and Comparative Examples 1 and 2

[0115] Rubber shown in Table 1 was first pelletized by a rubberpelletizer at about 100° C., and then rubber, a matrix resin, ageresistor, filler and tackifier were dry blended in blending ratios forExamples 1 to 10 and Comparative Examples 1 and 2, each of the resultingblends being injected into a double-screw kneader to be melt kneaded.Thereafter, and a vulcanizing agent was added from an intermediateinjection port to carry out dynamic vulcanization. At this point, thedouble-screw kneader was set at a temperature of 230° C. and a shearingspeed of 1,000 s⁻¹. Further, a moisture absorbent and an adhesivepromoter were injected from a final injection port of the double-screwkneader.

[0116] A thermoplastic elastomer composition extruded into a strand formfrom the double-screw kneader was cooled with water and pelletized by aresin pelletizer.

[0117] Two square glass sheets having 300 mm per side were fixed inparallel to each other at an interval of 6 mm, the above material waspaved in a space between the peripheral portions of the two glass sheetswhile it was extruded from a nozzle and molded to form insulating glass.The pellet was molded into a 30 μm-thick film by press molding as asample used for the measurement of water vapor permeability.

[0118] As for Examples 5 and 6, the thermoplastic elastomer compositionsprepared by the above method were dry blended with a barrier resinimmediately before extrusion molding for the formation of insulatingglass to form insulating glass by the same method as described above.

Comparative Example 3

[0119] Insulating glass was produced in the same manner as in the aboveExamples and Comparative Examples except that a vulcanizing agent forrubber was not added during blending.

[0120] (1) Water Vapor Permeability

[0121] Six liters of water which is half the volume of a stainless steelcup 60 shown in FIG. 6 is injected into the stainless steel cup 60. Anupper opening in the cup 60 is covered with a sample sheet 63 (30 μm inthickness) obtained by cutting the sample sheet obtained in Examples 1to 10 and Comparative Examples 1 to 3, a sintered metal plate 64 isplaced upon the top of the sample sheet 63, and they are fastenedtogether with a bolt 66 and a nut 67 through affixing member 65. Thiscup is left to stand in the atmosphere at a temperature of 25° C. andthe total weight of the cup is measured after 1 month. A reduction inthe weight of the cup per 24 hours is calculated and water vaporpermeability is calculated from the following expression water vaporpermeability [(g/24 hr·m²)]=M/(T·A) where A is a permeation area [m²], Tis a test time [day] and M is a weight reduction [g].

[0122] (2) The Heat Distortion Temperature (Load Deflection Temperature)of a Thermoplastic Resin used as a Continuous Phase is Measured at 0.45MPa in Accordance with JIS K 7207.

[0123] (3) Measurement of Dew Point

[0124] The dew point is measured after the end of the following testsbased on the test standards of classes I to III (classification byacceleration durability) specified in JIS R 3209.

[0125] class I: 7 days of moisture resistance and light resistance test+12 cycles of cooling and heating repetition test class II: 14 days ofmoisture resistance and light resistance test +24 cycles of cooling andheating repetition test class III: 42 days of moisture resistance andlight resistance test +72 cycles of cooling and heating repetition testIn the table, ◯ indicates that the dew point is −35° C. or less, Δindicates that the dew point is more than −35° C. and less than −30° C.and × indicates that the dew point is −30° C. or more.

[0126] (4) Dislocation at the Time of Processing

[0127] One glass sheet of the insulating glass produced in Examples andComparative Examples is fixed and a load of 8 kg is placed upon theother glass sheet to measure the amount of downward movement of theglass sheet that is loaded at a temperature of 50° C. A glass sheetwhich is moved 0.5 mm or less a day is expressed by ◯ and a glass sheetwhich is moved more than 0.5 mm is expressed by ×.

[0128] As a result, the thermoplastic elastomer composition as inComparative Examples 1 and 2 which is produced from the rubber orthermoplastic resin with more water vapor permeability has low steampermeation resistance, and when such a thermoplastic elastomercomposition is used to form insulating glass, it has a high dew pointdue to steam entry into the insulating glass through the seal.

[0129] Further, in Comparative Example 3, the amount of rubber was largeand the value of α₁ exceeded 1, so that the continuous phase formed byrubber and the dispersion phase formed by the resin were constructedinto layer. Since the rubber forming the continues phase has a low heatdistortion temperature, the rubber could not bear the load of glass atthe time of processing, resulting in dislocation. TABLE 1 (part 1)Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7matrix resin PET HDPE 30 30 30 30 30 30 50 PS rubber modified butylrubber 70 70 70 70 70 70 50 (Br-IPMS) EPDM IR barrier resin HDPE 10 20vulcanizing system ZnO 3.5 3.5 3.5 3.5 3.5 3.5 2.5 zinc stearate 1.4 1.41.4 1.4 1.4 1.4 1 stearic acid 0.7 0.7 0.7 0.7 0.7 0.7 0.5 sulfur NSphenol bromide age resistor RD 1.4 1.4 1.4 1.4 1.4 1.4 1 moistureabsorbing filler 50 50 50 zeolite 1 50 50 25 zeolite 2 50 fillertackifier adhesion promoter (epoxysilane) talc 50 50 50 50 50 50 50rosin ester 50 50 50 50 50 50 50 silane coupling agent 2 0.5 2 2 2 2 2steam permeability of resin*¹ 9 9 9 9 9 9 9 steam permeability ofrubber*¹ 82 82 82 82 82 82 82 heat deformation temperature of 112 112112 112 112 112 112 matrix resin (° C.) α₁ 0.93 0.93 0.93 0.93 0.93 0.930.40 α₁ — — — — 0.003 0.005 — η_(d)/η_(m) — — — — 3.8 3.8 —characteristic properties of material 38 37 38 38 25 16 24 steampermeability characteristic properties of multi-layer glass JIS R-3209class 1 ∘ ∘ ∘ ∘ ∘ ∘ ∘ class 2 ∘ ∘ ∘ ∘ ∘ ∘ ∘ class 3 ∘ Δ Δ ∘ ∘ ∘ ∘dislocation at the ∘ ∘ ∘ ∘ ∘ ∘ ∘ time of processing (part 2) ComparativeComparative Comparative Example 8 Example 9 Example 10 Example 1 Example2 Example 3 matrix resin PET 30 HDPE 70 30 30 5 PS 30 rubber modifiedbutyl rubber 30 70 95 (Br-IPMS) EPDM 70 70 70 IR barrier resin HDPEvulcanizing system ZnO 1.5 3.5 3.5 3.5 3.5 zinc stearate 0.6 1.4 0.7 1.4stearic acid 0.3 0.7 0.7 2.1 0.7 sulfur 1.4 Ns 0.7 phenol bromide 8.4age resistor RD 0.6 1.4 1.4 1.4 1.4 2 moisture absorbing filler zeolite1 50 50 50 50 50 50 zeolite 2 filler tackifier adhesion promoter(epoxysilane) talc 50 50 50 50 50 50 rosin ester 50 50 50 50 50 50silane coupling agent 2 2 2 2 2 2 steam permeability of resin*¹ 9 9 10 9840 9 steam permeability of rubber*¹ 82 157 82 1720 157 82 heatdeformation temperature of 112 112 191 112 88 — matrix resin (° C.) α₁0.03 0.93 0.98 0.90 0.89 7.6 α₁ — — — — — — η_(d)/η_(m) — — — — — —characteristic properties of 16 51 39 100 319 82 material steampermeability characteristic properties of multi-layer glass JIS R-3209class 1 ∘ ∘ ∘ ∘ Δ ∘ class 2 ∘ ∘ ∘ Δ ∘ class 3 ∘ ∘ ∘ x x ∘ dislocation atthe ∘ ∘ ∘ ∘ ∘ x time of processing

Examples 11 and 12

[0130] The thermoplastic elastomer composition of Example 1 as an innerlayer and maleic acid modified EEA or ethylene-vinyl acetate saponifiedproduct as an outer layer were co-extruded at about 200° C. to form aspacer and insulating glass was produced in the same manner as inExample 1. The thickness of the obtained adhesive layer was about 20 μm.

[0131] The characteristic properties of the insulating glass weremeasured and evaluated in the same manner as in Example 1. Results areshown in Table 2.

Example 13

[0132] A primer was prepared by dissolving an ethylene-vinyl acetatesaponified product in toluene in a solid content of 10% This primer wascoated on a glass sheet with a brush and left to stand for 15 minutesand then insulating glass was produced in the same manner as inExample 1. Thereafter, the characteristic properties of the insulatingglass were evaluated in the same manner as in Example 1. Results areshown in Table 2. TABLE 2 Example 11 Example 12 Example 13 thermoplasticmaterial of material of material of elastomer Example 1 Example 1Example 1 composition layer maleic acid ethylene-vinyl ethylene-vinyladhesive layer modified EEA actetate actetate saponified saponifiedproduct product coating of double-layer double-layer primer coatingadhesive coextrusion coextrusion molding molding characteristicproperties of insulating glass JIS R-3209 class 1 ◯ ◯ ◯ class 2 ◯ ◯ ◯class 3 ◯ ◯ ◯ dislocation Δ ◯ ◯ at the time of ◯ ◯ ◯ processing

[0133] <components in tables>

[0134] PET: J125 by Mitsui PET Co., Ltd.

[0135] HDPE (matrix): Hizex 2100J by Mitsui Chemical Co., Ltd.

[0136] PS: Stylon 666 R by Asahi Chemical Industry Co., Ltd.

[0137] modified butyl rubber: Exxpro89-4 by Eccson Co., Ltd.

[0138] EPDM: EPT 3045 by Mitsui Chemical Co., Ltd.

[0139] IR: Nipole 2200 by Nippon Zeon Co., Ltd.

[0140] HDPE (barrier resin): Ryubmer 5000 by Mitsui Chemical Co., Ltd.

[0141] ZnO: zinc oxide No. 3 by Seido Kagaku Co., Ltd.

[0142] zinc stearate: zinc stearate by Seido Kagaku Co., Ltd.

[0143] stearic acid: bead stearic acid by NOF Corporation

[0144] sulfur: powdery sulfur by Karuizawa Seirensho Co., Ltd.

[0145] NS: Nokusera NS by Ohuchi Shinko Kagaku Co., Ltd.

[0146] phenol bromide: Tackirol 250-1 by Taoka Kagaku Co., Ltd.

[0147] RD: Antigen-RD-F by Sumitomo Chemical Co., Ltd.

[0148] zeolite 1: Zeoram 4A by Tosoh Corporation

[0149] zeolite 2: Zeoram 3 by Tosoh Corporation

[0150] talc: Talc F by Nippon Talc Co., Ltd.

[0151] rosin ester: Pensel AD by Arakawa Kagaku Co., Ltd.

[0152] silane coupling agent: A-174 by Nippon Unicar Co., Ltd.

[0153] maleic acid modified EEA: AR-201 by Mitsui-Dupont PolychemicalCo., Ltd.

[0154] ethylene-vinyl acetate saponified product: Dumiran C1550 byTakeda Chemical Industries, Ltd.

Examples 14 to 16 and Comparative Example 4

[0155] A sealing material was produced according to formulations shownin Table 3 below in the same manner as in Example 1. The steampermeabilities of the used resin and the used rubber were 9 g/24 hr·m²and 82 g/24 hr·m, respectively, and the water vapor permeability of theproduced thermoplastic elastomer composition for sealing the insulatingglass was 38 g/24 hr·m². TABLE 3 Example matrix resin HDPE 30 Rubbermodified butyl rubber 70 vulcanizing system ZnO 3.5 zinc stearate 1.4stearic acid 0.7 Age resistor RD 1.4 moisture absorbing filler zeolite 150 filler talc 50 tackifier rosin ester 50 adhesive promoterethylene-vinyl acetate 10 copolymer saponified product

[0156] The sealing material produced by the above method had an MFR at230° C. of 100 g/min. The produced sealing material pellets wereinjected into a simplified extruder, a nozzle was inserted into a spacebetween two glass sheets at 230° C., and the sealing material wascharged into the space at a delivery rate of 2,000 g/min to produce thefollowing insulating glass production of insulating glass

[0157] size of glass sheet

[0158] thickness of glass sheet

[0159] type of glass sheet float glass

[0160] interval between glass sheets h: 6 mm

[0161] size of nozzle

[0162] H: 5 mm

[0163] L: 15 mm

[0164] l: 5 mm

[0165] S₁: 5 mm

[0166] S₂: 2 mm

[0167] Table 4 below shows experimental results obtained by thecomparison of the leveled surfaces of the sealing material W by theshape of the discharge port of the nozzle body 11 and adhesion to thesurface of glass between Examples 14, 15 and 16 of the present inventionand the prior art (Comparative Example 4).

[0168] As obvious from the experimental results, it has been found thatthe upper and lower leveled surfaces of the sealing material are betterand the adhesion of the sealing material to glass is better when theslide plate and the guide plate are provided at the leading end of thenozzle body 11. TABLE 4 Comparative Example 14 Example 15 Example 16Example 4 shape of discharge port of nozzle no sliding portion upper andlower upper surface Smooth Smooth almost smooth cut portion of leveled ⊚⊚ ∘ glass is not flat surfaces x lower surface Smooth almost smoothalmost smooth becomes wavy ⊚ ∘ ∘ x adhesion to glass surface adhered toalmost adhered almost adhered partly not entire surface to entire toentire adhered ⊚ surface surface ∘ ∘ Δ

[0169] The thermoplastic elastomer composition of the present inventionhas excellent steam permeation resistance and heat distortion resistanceand is suitable for use as the raw material of a sealing material andspacer for insulating glass when a thermoplastic resin and rubber havinga low water vapor permeability are used and the thermoplastic resin isused as a continuous phase.

[0170] The insulating glass of the present invention which uses thethermoplastic elastomer composition of the present invention as asealing material and spacer has excellent heat distortion resistance andan air layer having a sufficiently low dew point. Further, theinsulating glass of the present invention can be produced very easilybecause the number of production steps is much smaller than that of theconventional insulating glass.

[0171] Further, according to the process of the present invention, sincea sealing material is charged into a space between the peripheralportions of glass sheets using a production nozzle having a slide platewhich slides along the peripheral portions of a plurality of glasssheets at the top of the leading end portion of the nozzle body asdescribed above, the sealing material can be efficiently paved in thespace between the peripheral portions of the glass sheets and can bedirectly adhered to the glass sheets, and the sealing material at theperipheral portions of the glass sheets can be leveled to obtain goodappearance, and efficient work can be carried out by reducing the numberof working steps.

[0172] Further, the production nozzle of the present invention can beadvantageously used in this production process.

What is claimed is:
 1. A thermoplastic elastomer composition producedfrom a thermoplastic resin having a water vapor permeability of 100g/m²·24 h or less (30 μm in thickness) and rubber having a water vaporpermeability of 300 g/m²·24 h or less (30 μm in thickness) whencrosslinked, said composition having a dispersion phase formed of arubber composition at least part of which is dynamically crosslinked inthe continuous phase of the thermoplastic resin.
 2. The thermoplasticresin composition according to claim 1, wherein said composition furthercontains a moisture absorbent.
 3. The thermoplastic resin compositionaccording to claim 1, wherein the thermoplastic resin has a heatdistortion temperature of 50° C. or more.
 4. The thermoplastic resincomposition according to claim 1, wherein said composition furthercontains a barrier resin against steam permeation.
 5. Insulating glasswhich uses the thermoplastic elastomer composition of claim 1 as asealing material and spacer.
 6. The insulating glass according to claim5, wherein said insulating glass has an adhesive layer between thethermoplastic elastomer composition as the sealing material and spacerand glass sheets.
 7. The insulating glass according to claim 6, whereinthe adhesive layer is formed of an olefin/vinyl acetate copolymer.
 8. Aprocess for producing insulating glass by charging a sealing materialhaving a predetermined width into a space between the peripheralportions of at least two glass sheets which are opposed to each other inparallel at a predetermined interval to isolate a hollow layer from theoutside air, the process comprising the steps of: inserting in advancethe leading end of a charging nozzle into the space between theperipheral portions of a plurality of glass sheets; contacting a slideplate provided at the top of the leading end portion of the nozzle tothe peripheral portions of the plurality of glass sheets; dischargingthe sealing material from the leading end of the nozzle body at apredetermined rate; and moving at least one of the glass sheets and thenozzle body relative to the other to charge the sealing material intothe space between the peripheral portions of the glass sheets from theleading end of the nozzle.
 9. The process for producing insulating glassaccording to claim 8, wherein the sealing material at the peripheralportions of the plurality of glass sheets is leveled by the slide plateprovided at the top of the leading end portion of the nozzle body andthe lower side of the sealing material in the space between theplurality of glass sheets is leveled by a guide plate provided at alower end portion at the leading end of the nozzle body when the sealingmaterial is charged into the space between the peripheral portions ofthe glass sheets.
 10. A process for producing insulating glass whichuses the thermoplastic elastomer composition of claim 1 as a sealingmaterial and spacer.
 11. A nozzle for producing insulating glass byinserting the leading end portion of a nozzle into a space between theperipheral portions of at least two glass sheets which are opposed toeach other in parallel at a predetermined interval and charging asealing material from the leading end portion of the nozzle into thespace between the peripheral portions of the glass sheets while movingat least one of the glass sheets and the nozzle body relative to theother, wherein the leading end of the nozzle body has a width forpositioning the interval between the plurality of glass sheets and aslide plate which slides along the peripheral portions of the pluralityof glass sheets at the top of the leading end portion.
 12. The nozzlefor producing insulating glass according to claim 11, wherein the slideplate provided at the top of the leading end portion of the nozzle bodyprojects along the discharge direction of the sealing material.
 13. Thenozzle for producing insulating glass according to claim 11 or 12,wherein a guide plate is formed at the lower end portion at the leadingend of the nozzle body inserted into the space between the plurality ofglass sheets in such a manner that the guide plate projects parallel tothe slide plate and along the discharge direction of the sealingmaterial.